Lubricant and method of lubrication



Patented July 2, 1940 it Our invention relates to lubricating oils andmore particularly to improved methods for the production of high qualitylubricating oils and such products as new compositions of matter.

This application is a continuation in part of our copending applicationsSerial No. 733,862, filed July 5, 1934, and Serial No, 116,986, filedDecember 21, 1936, now Patent No. 2,137,777 of November 22, 1938. p

Engines are being designed for higher pressures on rubbing surfaces, andit is well known that mineral lubricating oils are deficient in extremepressure characteristics. With greater pressures at rubbing surfaces nowbeing employed, the very best quality hydrocarbon lubricants will breakdown and allow metal-to-metal contact with subsequent seizure andfailure of the rubbing surfaces. This condition of lubrication isreferred to as boundary lubrication and may obtain when engines areoperating at heavy loads, low speeds, or if for any reason the supply oflubricant is cut off or not suflicient. This last condition may existwhen, for mechanical reasons, the lubricant pump is not functioningproperly or when the lubricant feed line is clogged with foreign matter.

One object of our invention is to provide a lubricant of low coefficientof friction and one which will act as a safety factor in lubricationwhen abnormal conditions exist for onereason or another. Another objectof our invention is to produce a lubricant of high film strength orextreme pressure characteristics which will allow operating enginessafely with much higher designed pressures on the rubbing surfaces.

Another object of our invention is to provide a lubricant which willmaintain a very low coefiicient of friction and high film strength whendiluted with light, as well as heavy hydrocarbon I lubricating film onthe rubbing surfaces at all times which is of particular value in thestarting of engines during cold weather when the lubricant is veryviscous and sluggish and the time required for delivering the lubricant.to the rubbing surfaces for viscous lubrication extended.

Still another object of our invention is the production of anextremepressure lubricant which is eflicient but not objectionablycorrosive or chemically active under conditions of use. This is a veryimportant factor, as it is possible to produce lubricants which, whilemore halogenated alcohols I 2 6 1 "UNITED STATES PATENT OFFICE-LUBRICANT AND METHOD OF LUBR-IOATION.

No Drawing. Application September 16, 1938, Serial No. 230,338

22 Claims. (01. 252-58) able to carr ver hi loads without rupture of theoil filfn, ai e'ali o sufiieiently active chemically to have adeleterious action upon the metal parts with which they come in contact.I

The method which we have discovered and the lubricant prepared'therebyfor accomplishing the above objects consists broadly of adding one or tomineral hydrocarbon lubricants. We have found that halogenated alcoholsin lubricating oil provide lubricants of low coeflicient of friction,high film strength, and

which are not corrosive or chemically active to an ob ectionabl'edegree.

In practicing our invention, only small quantities, relatively speaking,of the various halogen- I Roller Bearing Company. The testing machinemay be operated under well-controlled conditions and at varying loads.The engine is so designed .that the load may be imposed upon a rotatingring pressured against a standard block. By the use of weights and aloading .ar'm, increasing pressures may be used until a point is reachedwhere the pressure is suflicient to rupture the' lubricating film andallow seizure of the ring and block. All conditions are held constantthroughout the test with the exception of load. It is possible by meansof this test to take any two lubricants and determine the load carryingcapacity of each for comparative purposes.

In our test work we have used very high quality that our invention isnot limited to the examples given Example No. 1

One percent (1%) of alphachlorhydrin added, to the above described S. A.E. '40 lubricant and tested on the Timken machine gave a film strength 3of 21,000 pounds per square inch It was obvious during the operation ofthe Timken machine with this lubricant-that the torque or coeflicient offriction was lower than with the mineral oil. Upon examination of thering and block after completing the test, no signs of excessive chemicalactivity could be noticed.

Example No. 2

A sample of commercially pure octadecyl alcohol was chlorinated bydirect chlorination until it contained suflicient chlorine to representthe dichlor product, and this material was air-blown to remove excessivechlorine and then given a slight alkali sulfite wash to remove anylabile and/or free chlorine and/or free hydrogen chloride existing inthe product. One per cent (1%) of this material was added to an S. A. E.30 mineral oil lubricant of very high quality which had a film strengthof 6,000 pounds when tested on the Timken machine. The blend of S. A. E.30 and octadecyl alcohol containing two atoms of chlorine per moleculegave a Timken film strength of 24,750 pounds per square inch. During thetest of the last mentioned lubricant on the Timken machine a very lowcoeflicient of friction was indicated by low torque and no visible signof excessive chemical activity could be noted at the end of the test.

Example No. 3

A sample of commercially pure stearic acid was reduced to thecorresponding alcohol by the usual laboratory method and theresultingmaterial chlorinated by direct chlorination until the product containedsufficient chlorine to represent the dichlor product. After removing theundesirable impurities by air-blowing, water-washing and a lightstabilizing treatment with sodium sulfite, this material was added to agood quality hydrocarbon lubricant of S. A. E. 30 classification andtested on the Timken machine. The S. A. E. 30 lubricant used in thistest was of the same quality as that used in Example No. 2 above. Thelubricant after the addition of the chlorinated reduced acid gave aTimken film strength of approximately 25,000 pounds per square inch andshowed very constant-low coeflicient of friction and no excessivechemical action.

Example No. 4

High molecular weight petroleum hydrocarbons, such as petroleum wax, maybe oxidized by I any of the many well-known methods, and the alcoholsresulting from such oxidation separated and halogenated for use in thisinvention. It is also possible to separate the acid formed by oxidationof petroleum hydrocarbon waxes and the like and reduce these to alcoholsby any of the well-known methods of reducing such material. Alcoholsproduced frorr. the oxidation and/ or oxidation reduction ofhydrocarbons when halogenated until they contain from about 5 to 50% ofchlorine by weight may be very successfully used in our invention. Usingcommercially 'pure products we have improved the film strength ofhydrocarbon lubricants by as much as 200 to 300 per cent by the additionof one per cent of the halogenated alcohol oxidation products ofpetroleum hydrocarbons.

-molecular weight esters found in animal and vegetable material uponhalogenation have been found to be very satisfactory for use in our. in-

vention. For example, the high molecular weight alcohols from thehydrolysis of beeswax, carnauba wax, s'permaceti, and the like uponchlorination are quite satisfactory for use within this invention. Thehigh molecular weight acids resulting from the hydrolysis of thesenaturally occurring materials may be reduced to alcohols by any of thewell-known means and halogenated for use in our invention.

Example No. 6

Olein alcohol resulting from the reduction of oleic acid by thewell-known means upon halogenation has been found satisfactory forimproving the film strength of good quality hydrocarbon lubricants andis quite satisfactory for use in our invention.

Example No. 7

Commercially pure myricyl alcohol was chlorinated until it containedsuflicient chlorine to be dichlor myricyl-alcohol. One per cent byvolume of this product, after satisfactory purification, was blendedwith the S. A. E. 30 lubricant previously mentioned and gave a Timkenfilm strength of 24,500 pounds per square inch. No signs of corrosivechemical activity were noted during or after the Timken test on theblock or ring.

Example No. 8

The aromatic alcohols, such as benzyl alcohol, ortho,. meta and paratolyl carbinol, and their substitution products, after halogenation, aresatisfactory in our invention. The halogen may be attached to thebenzene ring or attached to the side chain.

Other halogenated aromatic alcohols suitable for use in our inventionare chlorinated diphenyl-.

Halogenated propyl' alcohols Halogenated butyl alcohols Halogenated amylalcohols Halogenated hexyl alcohols Halogenated pentamethylene glycolHalogenated hexamethylene glycol Halogenated sym. dimethyl ethyleneglycol Halogenated sym. ethyl methyl ethylene glycol Halogenated unsym.dimethyl ethylene glycol Halogenated trimethylene glycol Halogenatedtetramethylene glycol a-chlorhydrin fl-chlorhydrin a-dichlorhydrinfi-dichlorhydrin Halogenated pentaglycerol aldehyde Halogenateddehydroxyacetone Other alcohols, on up through alcohols of as high as 50carbon atoms are perfectly satisfactory. Alcohols such as secondarybutyl alcohol,

isobutyl alcohol, and tertiary butyl alcohol, and

the other isomeric alcohols of carbon atoms 2,206,578 ranging from 3 to50 carbon atoms or above are aliphatic unsaturated alcohols containingfrom 3 to 50 carbon atoms or more and their isomeric compounds aresatisfactory for use in our invention after. halogenatiom.

The halogenated cycloaliphatic alcohols form another class coming withinthe scope of the present invention. The following isa list of' a fewtypical examples:

Most of the previously mentioned alcohols have been of the monohydrictype, but it is to .be understood that our invention includes dihydric,trihydric, and poly-hydroxy alcohols containing from 3 to 50 carbonatoms or' more after halogenation.

and be satisfactory foruse in our invention. Themono, di, and trihalohydrins may be used. This invention does not contemplate coveringany particular method of halogenating alcohols,

as any of the well-known methods have been found satisfactory.

It will be observed that throughout the foregoing specification, we havegiven a, rather large number of specific examples of materials whichmaybe used in compounding lubricants in accordance with our invention.

As indicated, these will generally be employed in conjunction withmineral lubricating oil of a lubricating viscosity and it will be foundthat certain of these named specific examples are rather difilcultlysoluble in the oil or soluble to only a limited extent. In using thesematerials, amutual solvent may be employed or the use of lubricantscontaining the same may be restricted to such cases where the hightemperature under which the lubricant'is ordinarily employed willmaintain the addition agents in solution. Likewise, otherswhich arequite volatile may be employed only in lubricants which are used, forexample, at relatively low temperatures so that the addition agent willnot bevolatilized from the oil body in which it is employed. v

Various means of purifying the halogenated alcohol may be employed, suchas water-washing,

air-blowing, alkali-washing, alkali-oxidizlng-reducing solution washing,passing through active charcoal, distillation under reduced pressure,steaming;.and the like, and combinations of two or more of these meansmay be employedin purifying the product prior to the addition of thematerial tolubricating oils.

The examples given have been limited to the chlorine containinghalogenated alcohols, but it is to be understood thattheother members ofthe halogen family are considered within the am- 7 bit of our invention.Fluorine is expensiveand highly active chemically, and. iodine andbromine are, as a rule, considered too expensive butmay be used in ourinvention. 10r i ne is. readily available at reasonablev prices and issatisfactory as a halogen for use in our invention.

It is believed that under conditions of extreme pressure, thehalogenated addition agents of this invention react chemically orphysico-chemically with the metallic surfaces to form a non-fluxingsurface which will not seize or score. This invention is n'ot'intendedto be limited, however, by any particular theory or explanation of theaction upon the metallic surfaces.

When using poorer quality, original hydrocarbon lubricants, largerquantities of halogenated alcohols may be required to obtain the desiredresults. With any given hydrocarbon lubricant, one skilled in the art ofpreparing the lubricants can'easily determine the percentage ofhalogenat ed alcohol required to give the necessary film strengthproperties, low coefiicient of friction properties, et cetera. In mostcases, the quantity will vary between .1% and 15% by volume. In

order that the viscosity of the finished lubricant may not be toogreatly diminished, amounts up to 20% by Weight, based on the amount oflubrieating oil, of the addition agent are contemplated by thisinvention and generally not more than 10% will be required. Quantitiesas low as about .1% often give noticeable improvement and about 3% isusually highly satisfactory.

Our invention is not limited tothe addition of halogenated alcohols tolubricants of S. A. E. 30 and S. A. E. 40 classification, as ourmaterials may be added to lubricants of all types, regardless 'ofclassification. Our materials are efficient for pheric at 140? andpreferablyat 170 C.

use with synthetic lubricating oils, hydrogenated lubricating oils,solvent extracted lubricating oils, and lubricants of all other typesand classes including other oils of lubricating viscosity such as animaland vegetable oils, namely, corn oil, cottonseed oil, lard oil, castoroil, sperm oil, shale oil and the like; also including greases orsoapthickened lubricants- It is also within the contemplation of thisinvention, to provide the addition agents in the form of a concentratein a suitable 011, said oil containing rather high percentages of theaddition agents. Such concentrates may be employed for future blendingwith a lubricating oil in the proportions desired for the particularconditions of use. 7 v

As, in general, the addition agent-will volatilize the more easily thelower its vapor pressure, this invention contemplates the use ofhalogenated alcohols having vapor pressures less than atmos- It .will beunderstood that certain features. sub-combinations are of utility and,may be employed without reference to other features andsub-combinations. is contemplated by and is with-.. the scope of ourclaims. It is further obvious that various changes may be made indetails within the-scope'of our claims without departing from the spiritof our invention. It

is, therefore, to be understood that our invention is not to be limitedto the specific details shown and described.

Halogenation and chlorination, as used herein, is meant to include anymeans or process 15 We, therefore, particularly point out and dis-,

tinctly claim as our invention:

1. A lubricating oil comprising in combination a major proportion of ahydrocarbon oil and a minor proportion of a halogenated alcohol.

2. A lubricant comprising in combination a major proportion of an oil oflubricating viscosity and a minor proportion of a halogenated alcohol.

3. A lubricating oil comprising in combination a a hydrocarbon oil and asmall amount of a chlorinated alcohol.

4. A lubricating oil comprising -in combination a major proportion of ahydrocarbon oil and a minor proportion of a halogenated armoaticalcohol.

5. A lubricating oil comprising in combination a major proportion of anoil of lubricating viscosity and a minor proportion of a chlorinatedaromatic alcohol.

6. A lubricating oil comprising in combination a major proportion of ahydrocarbon oil and a minor proportionof a halogenated cycloaliphaticalcohol.

7. A lubricating oil comprising in combination a major proportion of; anoil of lubricating'viscosity and a minor proportion of a chlorinatedcycloaliphatic alcohol.

8. A lubricating oil comprising in combination a major proportion of ahydrocarbon oil and from about 0.1% to 20% by weight, based on theamount of oil, of a halogenated alcohol having a vapor pressure lessthan atmospheric at 140 C.

9. A lubricating oil comprising in combination a hydrocarbon oil andfrom about 0.1% to 20% by weight, based on the amount of oil, of achlorinated alcohol having a vapor pressure less than atmospheric at 140C.

10. A lubricating oil comprising in combina-' tion a major proportionof'a hydrocarbon oil and from about 0.1% to 20% by weight, based on theamount of oil, of a halogen-bearing aromatic alcohol having a vaporpressure less than atmospheric at 140 C.

11. A lubricating oil comprising in combination a major proportion of ahydrocarbon oil and from about 0.1% to 20% by weight, based on theamount of oil, of a chlorine bearing aromatic alcohol having a vaporpressure less than atmospheric at 140 C.

12. A lubricating oil comprising in combina- It is also to be noted tiona major proportion of a hydrocarbon oil and. from about 0.1% to 20% byweight, based on the amount of oil, of a halogen-bearing cycloaliphaticalcohol having a vapor pressure less than atmospheric at 140 C.

13. The method of reducing friction between relatively moving metallicsurfaces which com-1 prises chemically acting upon such surfaces bymeans of a halogen-bearing alcohol contained in an oil havinglubricating viscosity.

14. A lubricating oil comprising in combination a lubricating oil baseand from about 0.1% to 3% by weight based on the amount of oil base, ofa halogen-bearing alcoholhaving a vapor pressure less than atmosphericat 140 C.

15. A lubricating oil comprising in combination a lubricating oil baseand. from about 0.1% to 3% by weight based on the amount of oil base, ofa halogen-bearing alcohol having a vapor pressure less than atmosphericat 170 C.

16. A lubricating oil comprising in combination a lubricating oil baseand from about 0.1% to 3% by weight based on the amount of oil base, ofa halogen-bearing aromatic alcohol having a vapor pressure less thanatmospheric at 140 C.

17. A lubricating oil comprising in combination a lubricating oil baseand from about 0.1% to 3% by weight based on the amount of oil base, ofa. chlorine-bearing aromatic alcohol having a vapor pressure less thanatmospheric at 170 C. l

18. A lubricating oil comprising in combination a lubricating oil baseand from about 0.1% to 3% by weight, based on the amount of oil base, ofa halogen-bearing cycloaliphatic alcohol having a vapor pressure lessthan atmospheric at 19. A lubricating oil comprising in combination alubricating oil base and from about 0.1% to 3% by weight, based on theamount of oil base, of a chlorine-bearing cycloaliphatic alcohol havinga vapor pressure less than atmospheric at 140 C.

20. A lubricating 011 comprising in combination a'lubricating oil baseandfrom about 0.1% to about 20% by weight, based on the amount of oilbase, of a halogen-bearing benzyl alcohol.

21. A lubricating oil comprising in combination a lubricating oil baseand from about 0.1%

to about 20%. by weight, based on the amount of oil base, ofhalogen-bearing cyclohexanol.

22. A lubricating composition comprising in combination a lubricatingoil base and from about 0.1% to about 20% by weight, based on the amountof oil base, of a mixture of halogen bearing alcohols derived from thehalogenation of the alcohols produced by the controlled oxidation ofpetroleum hydrocarbons.

- BERT H. LINCOLN. WALDO L. S'I'EINER.

ALFRED HENRIKSEN, By JOHN W. WOLFE, Administrator de bonis non of theEstate of Alfred Henriksen, Deceased.

